Preparation of phenylchlorosilanes



williann-Asschwenker, Scotlmilhflg,assignortm "General, EI'ecthi'c-I Gompanm; a corporation ire Drawing-i. :mueaummm-en s, r951,

:seoaruo. 213,801

, inuentiomisi use. of; phenxlchlomsilanesi, Ma n tream ng.

the: invention; relates: to rev-process for: preparing phenylchlorosilanesv which. comprises passing chlorobenzene in the presence-ofaaasmallsamount on sodium .chloridaoven. eommerciab silicon. (2on taining traces of? aluminum. at an elevated: tern; v perature, preferably in ther; presence o1 raicats a alystfor the-reaction r-Ro'chow Patent asaosesiss'uee August-1,1945

and, assigned; to thewsame assignee as the present invention discloses the preparation otjphenyl ehlorosi-lanes, for: example, phenyltrichlorosilane; diphenyldichlorosilane, etc *by the passage of chlorobenzene-,, specifically: monochlorobenzene, over. silicon, The, temperaturesemnloyed-i-in such reactions are of the ordenotrfrom about zfitli Cote below: the decomposition point of, the-ingredients.

or the formed reaction; product-tas ier example;-

action which cleaves. thQtQhBDfiljjQl'QllPSsftOHli the silicom'atoms. Although: it is notrabsolutelya-cera-j tain; what, has: .caused this'decompositiomiotthe phenylchlorosilanesg nevertheless it is believed that such: decomposition. may be due-toi the-presence; of small amounts ofrahim-inunrin thecommercial; silicon: which: is ordinarilwemployedr in the reaction This al'uminunris believedz-tor'combine: withchlorine found during; the: reactionv to form aluminum chloridey'szandi ltL'il S this --;latter aluminum; chloride: which; is hel-ieved;to: cause the cleavage of: the phenyl groups. :Because of this cleavage, there have; been: reduced: -,yi'e1ds Mot phenylchlorosilanes as." wel-l as 1 the r necessity tor added distillations in ordentomemove-decompositionproducts from: the reaction; product; containingqthe desired phenylchiorosilanes:

I have now discovered that ultimate-improved, yields; of 1 phenylchlorosilames produced-shy the passage of chlorobenzeneoveio finelwdiviiierbcome mercialfsiliconcan be, obtained by employing small amounts of sodium chloride with the silicon powder. This improyement'm ultimate yield'of phenylchlorosilanes results from the fact that there is little, if any, decomposition of the iormed phenylchlorosilanes during subsequent distillat'ioi'i'and isolation thereof, thus requiring fewer distillation steps. I

Additionally, it has been found that after the silicon-catalyst powders have been used to sub stantial exhaustion, the presence of the sodium chlorideadecreasesz m powder:to; cake-laud plue whichheretotorawas aserious disadvantageprion" reactions between the ingredients --Eina- 1l y, it wasfoundthat afterv the! reactionwas completed, theipresenceof the; sodium .=chl oride permitted voiding -thef reactor 01 theusiliconscatalyst powders readily" without: re-v quiringannmechanical prodding, I

- .Theramount zot sodium chloride employediisi fairly smalb. and: mayranges for instances; from about-lute; 101%. by- -weight,. preferably: from 2" to firper: cent, based onztheaweigh-t of the silicon. The silicon: powder the usual commercial. powder-employed: such reactions which contains about 0.12110: Zrpercent, by=weight,- thereof aluminumlxincluding fractionai-rsmallzamountsmf other impuritiestas, fot'examplm, iron calcium, man-- ganese; etc Generally; 1:prefertoemploya;commercial: silicon powder: which comprises at? least: 75%silicon. vIn:thisircspect,l3 may usesueh sil' icompowders: as essentially pure silicon-contains ing. only-aluminum: as the"impurity or silicon-1m: combination with metalsrsuchzas iron si'lven; etc. Generallwcommercialx silicon. employed". in the abovesdescr-ibed reaction containsat' least 97" per cent silicon: v i

' carrying-out the invention, many-bf: theconditions; which are more: particularly disclosed or- 3 taught "in theaaforementionedi Rochow" patent mag -be employe'd and the? latterpatent because" ofit's morethan -adequatez disclosure:- is made a; part of thepresent disclosures;v The catalyst maycomprise from about 0.2 to 25 per cent;.by" weight; based-on the total weight: of the: silicon and the catalyst, Generally, the catalystv andv silicon powders are mechanically mixed together to:form a homogeneous'mixture and placedin' thereactor so that; the chlorobenzene'may be passed: through. suchpowd'en'. It hasv beeir found advantageous t'o heat the chlorobenzene so that. the temperature of reaction-ranges" from about 250 to 600 0., es g-.,--"from' 30I0 to 575 C., and the reaction betweenthechiorobenzene"and thersiliconiseffected' while thechlorobenzen'e is inthe vapor phase.

Varying pressure conditions, for example, atmos-- pheric or superatmosphericconditions may: be employed and- -I- have found thatfsomewhat increased yieldsare realized when pressuresof the order of about to -500 p. s, 1. are used duri-ng'thereaction; 1

"ru ers-wiser thoseskili'edin the -a'rt" may better understand how the present invention may be practiced, the following example is given by way of illustration and not by way of limitation. All parts are b n-weight. The reactor used in each of the instances'described below was a 6" inside diameter reactor, 10' long of the "fluidbed type having a diffuser plate at the bottom to distribute the gas feed evenly, and a porous new theten'dencyoI the awasu 3 ceramic filter at the top to separate entrained solids from the product gas stream, was done by means of a jacket through'which hot flue gas was circulated.

Example 21-; In this example, the powder chargeemployed comprised 60 parts of powder (about 200 mesh or finer) of which 2%, by weight, was'finely divided silver powder and 98%, by weight, -=was may divided commercial silicon (97 per cent silicon,

and fractions of one per cent of iron, manganese,

and calcium, and containing from 0.71 to FI- per parts per hour while the temperature of the re-" actorwas maintained at about 550 -C. and the pressure therein was about 100 p; s. i. The length: of'the reaction run was about l2 hours; Asa control, another reaction was conducted under essentially the same conditions with the exception no sodium chloride had caked and plugged up so so thatit was necessaryto use mechanical force to aid' in removal of the 'sili'conesilv'er mass.

' It will, of course, be apparent 'to' those skilled in the art that other types of commercial silicon powders containing varying amounts of alumi- ;num' and different particle sizes, many of which are described in the aforementioned Rochow Patentandflin 'Gilliam et al. Patents 2,466,412 and 2,466, 113.,both,issued April 5, 1949, may be employed without departing from the scope of theinvention? The silicon may be in the form of finely divided silicon intermixed with the finely dividedcatalyst, or it may be alloyed with the that no sodium chloride was added to the mix ture of silicon and silver powders. Each reaction product was then fractionally distilled until the pot temperature was around 240 to 250 C. Thereafter, to determine the degree of decomposition, each residue was refluxed under heat at atmospheric pressure for 5 hours. .During these refluxingsfthe mixture containing sodium chloride showed little if any drop in head temperature and the amount of decomposition of the phenylchlorosilanes was of the order of at most about 0.2 percent of the amount of phenylchloro-' silanes in the mass. 'In contrast to this, the re-'- fluxed mass derived from the reaction product free of sodium chloride showed alarge drop in head temperature (of the order of about 14' degrees) due to the formation of low boiling-decomposition products, namely e. g., benzene and SiCli", and the amount of decomposition of the phenylchlorosilanes was of the order of about 5.1

per cent on the same basis as above. In addition,

after removal of the lower boilers up to and including chlorobenzene, subsequent distillation of the Z residues .to obtain phenylchlorosilanes, (e. g., phenyltrichlorosilane, diphenyldichlorm' silane, etc.), in the case of the original reaction product containing sodium chloride, resulted in a substantiallycolorless, overhead product of phenylchlorosilanes uncontaminated with low boiling-decomposition, products.- Incontrast to this, distillationof the residue from the reaction ticles of solid material to flOWiIOmthe-reactor. q

In contrast to this-the reactor which contained powder;

catalyst and thereafter powdered to give a hamqean s nely divided powder had to whi the sodium chloride may" be added Such alloys are more "particularly disclosed -and" claimed in Rochow 'et al. Patents 2,380,996 and 2,383,818 as well as in the aforementioned Gilliam et a1.

meat .466. 1

-It wil1 be apparent that the amount of sodium chloride may also be varied and generally should comprise'an amount'thereof'suificient to reduce decomposition of the formed phenylchlorosilanes to as small a value as-possible'. This will'advantageously call for an amount" of sodium chloride at least molarly equal toand preferably in' excess of (for example, from 1 to 4 times) the molar concentration of the aluminum in the silicon V The temperature and pressure conditionsmay also be'modified to suit the available apparatus and conditions; 4

What I'claim as new and desire to secure by Letters Patent in the United States is: i l'; Themethod 'of making phenylchlorosilanes which comprises passing at an el'evatedtemperature chlorobenaenebver a contact mass compris ing finely divided commercial silicon containing traces of aluminum, therebeing present in the powderfro'mfabout- 1 to 10%, by weight, sodium chloride,'based on the weight of the silicon; The process which comprises passing 'at an elevated; temperature 'monochlorobenzene over a contact mass' comprising a mi'x'tur'e"'of finely dividedpowders containing a preponderant amountfof finely divided aluminum-containing commercial silicon' 'a'nd a'minor proportion of finely dividedsilve'r'powder', the'said mixtures of powders containing 1 to 10 byweight, sodium chloride, based 'onthe weight of the silicon.

3'; The process as in claim 2 'wherein the tern-- perature at which the reaction is carried out is fromabout 250 to' 575' C. Y

a. A contactmass for making phenylchloro silanes from the chemical reaction between sili= con'and chlorobenzene, said contact mass comprising essentially finely divided aluminum-contaming-commercial silicon, a minor proportion of a catalyst for the reaction, and from 1 to 10%, by weight, sodium chloride, based onthe weight of the silicon.

A' contact mass, as. in claim 4 wherein the catalyst comprises flnelydivided silver powder.

' No references cited. 

1. THE METHOD OF MAKING PHENYLCHLOROSILANE WHICH COMPRISES PASSING AT AN ELEVATED TEMPERATURE CHLOROBENZENE OVER A CONTACT MASS COMPRISING FINELY DIVIDED COMMERCIAL SILICON CONTAINING TRACES OF ALUMINUM, THERE BEING PRESENT IN THE POWDER, FROM ABOUT 1 TO 10%, BY WEIGHT, SODIUM CHLORIDE, BASED ON THE WEIGHT OF THE SILICON. 